CN106700033B - A kind of cationic visible light solidified composition - Google Patents
A kind of cationic visible light solidified composition Download PDFInfo
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- CN106700033B CN106700033B CN201510794489.9A CN201510794489A CN106700033B CN 106700033 B CN106700033 B CN 106700033B CN 201510794489 A CN201510794489 A CN 201510794489A CN 106700033 B CN106700033 B CN 106700033B
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Abstract
The invention discloses a kind of cationic visible light solidified compositions, it includes the bisphenol A type epoxy resin of the initiator of 0.5~10 parts by weight, the reactive diluent of 0.5~30 parts by weight and 70~90 parts by weight, wherein, initiator include weight ratio be 1:(0.01~1) cation light initiator and sensitizer；Cationic visible light solidified composition provided by the invention can under the irradiation of visible light curing molding, low for equipment requirements, cost is lower, and safety is higher, and environmental pollution is smaller, photosensitive strong, and photocuring high conversion rate, is being less than 30mW/cm2Low-light (level) under its solidify conversion ratio up to 50%, the velocity of initiation of initiator is fast, high-efficient, with good stability, and toxicity is low, no pollution to the environment, and cheap and easy to get, at low cost.
Description
Technical field
The invention belongs to light polymerization technique fields, and in particular to a kind of cationic visible light solidified composition.
Background technique
Bisphenol A type epoxy resin is the smallest one kind of cure shrinkage in thermosetting resin, itself is had very high viscous
With joint efforts, solidifying manufactured goods has excellent mechanical performance, chemical resistance and electrical insulation capability, and cheap, extensively
Applied to multiple fields such as adhesive, rapid shapings.Traditional handicraft mainly uses heat cure forming technique to solidify it, but
It is complex process, at high cost.
With the development of epoxy resin light radiation curing molding technology, the photocuring of bisphenol A type epoxy resin is studied
There are some progress, is concentrated mainly in the UV curing system of bisphenol A type epoxy resin.But ultraviolet source to equipment have compared with
High request, radiation is big, environmental safety is poor, and solidification is at high cost, significantly limits its application.
Therefore, the bisphenol A type epoxy resin visible-light curing system that exploitation is safer, at low cost, pollution is small, which has, grinds
Study carefully value and practical significance.
Summary of the invention
In order to overcome the above problem, the present inventor has carried out sharp study to photocuring technology, prepares a kind of cation
Type visible light solidified composition uses specific structure and the cationic initiator of content to cooperate sensitizer, can be in visible light
Irradiation under cause bisphenol A type epoxy resin curing molding.
The purpose of the present invention is to provide a kind of cationic visible light solidified compositions comprising following weight proportion
Component:
0.5~10 parts by weight of initiator；
0.5~30 parts by weight of reactive diluent；With
70~90 parts by weight of bisphenol A type epoxy resin,
Wherein, the initiator includes cation light initiator and sensitizer.
The weight ratio of the cation light initiator and sensitizer is 1:(0.01~1), preferably 1:(0.05~0.8),
More preferably 1:(0.25~0.5).
The cation light initiator is the diaryl iodonium salt as shown in formula (I).
Wherein, R1Selected from-H ,-R ' and-OR ', R ' be C1-12Alkyl；
X-Selected from SbF6 -, AsF6 -, PF6 -And BF4 -。
The sensitizer has the structure as shown in formula (II).
Wherein, R2、R3、R4Selected from-H ,-R " ,-OR " and-Br, and R2、R3、R4In at least one be-Br, R " be C1-12
Alkyl.
The epoxide number of the bisphenol A type epoxy resin is 0.35~0.57, preferably 0.41~0.52.
Composition as described above comprising the component of following weight proportion:
The reactive diluent is selected from one of epoxy alkyl chloride, alkyl chloride, ketone and heteroaromatic compound or several
Kind.
Under visible light source irradiation polymerization reaction, curing molding occur for the composition.
The wavelength of the visible light source is 380~600nm.
Beneficial effect possessed by the present invention includes:
(1) cationic visible light solidified composition provided by the invention can under the irradiation of visible light curing molding,
Low for equipment requirements, cost is lower, and safety is higher and environmental pollution is smaller；
(2) cationic visible light solidified composition provided by the invention is photosensitive strong, and photocuring high conversion rate,
Less than 30mW/cm2Low-light (level) under its solidify conversion ratio up to 50%；
(3) specific cation light initiator and increasing are used in cationic visible light solidified composition provided by the invention
Feel initiator of the agent as photocuring reaction, velocity of initiation is fast, high-efficient, with good stability, and toxicity is low, to environment
It is pollution-free and cheap and easy to get, it is at low cost.
Detailed description of the invention
Fig. 1 shows the UV-visible absorption spectrum that experimental example 1 measures；
The epoxy conversion ratio obtained Fig. 2 shows experimental example 2 with light application time change curve；
Fig. 3 shows epoxy conversion ratio that experimental example 3 obtains with the change curve of light application time.
Specific embodiment
Below by attached drawing, experimental example and embodiment, the present invention is described in more detail.Illustrated by these, the present invention
The characteristics of and advantage will become more apparent from it is clear.
According to the present invention, a kind of cationic visible light solidified composition is provided comprising the component of following weight proportion:
0.5~10 parts by weight of initiator；
0.5~30 parts by weight of reactive diluent；With
70~90 parts by weight of bisphenol A type epoxy resin,
The initiator includes cation light initiator and sensitizer, wherein the cation light initiator and sensitizer
Weight ratio be 1:(0.01~1), preferably 1:(0.05~0.8), more preferably 1:(0.25~0.5).
In a preferred embodiment in accordance with the present invention, the cation light initiator is the diaryl as shown in formula (I)
Salt compounded of iodine can absorb the energy of certain wavelength in ultraviolet region, generate cation, to cause epoxy monomer or epoxy is pre-
Polymerization reaction crosslinking curing, a length of 250nm of maximum absorption wave or so occur for aggressiveness.
Wherein, R1Selected from-H ,-R ' and-OR ', R ' be C1-12Alkyl, it is preferable that R1Selected from-H and C1-6Alkyl.
X-Selected from SbF6 -, AsF6 -, PF6 -And BF4 -, preferably PF6 -Or BF4 -。
It is highly preferred that the cation light initiator is diphenyl iodine hexafluorophosphate (as shown in formula (III)), 4,4 '-
Dimethyl diphenyl iodine hexafluorophosphate, diphenyl iodine tetrafluoroborate or 4,4 '-dimethyl diphenyl iodine tetrafluoro boron
Hydrochlorate.
Above-mentioned initiator is known compound, can be commercially available, can also synthesize to obtain according to existing method, herein not
It repeats.
In a preferred embodiment in accordance with the present invention, the sensitizer is the BODIPY (boron fluoride as shown in formula (II)
Two pyrroles) fluorochrome, there is relatively strong absorption, a length of 540nm of maximum absorption wave or so, above-mentioned sensitizer in visible region
After mixing with the cation light initiator as shown in formula (I) according to special ratios, sensitive volume can be made to be extended to entire visible light
Region, so as to cause the cross-linking and curing reaction of epoxy monomer or epoxy prepolymer using visible light.
Wherein, R2、R3、R4Selected from-H ,-R " ,-OR " and-Br, and R2、R3、R4In at least one be-Br, R " be C1-12
Alkyl, preferably C1-6Alkyl.
It is highly preferred that the sensitizer is the BODIPY fluorochrome as shown in formula (IV) or formula (V).
Sensitizer used in the present invention is referred to known method synthesis and obtains, the method referring to RSC Advances,
2012,2,9851-9859。
The bisphenol A type epoxy resin has the structure as shown in formula (VI), and epoxide number is 0.35~0.57, preferably
0.41~0.52.
Wherein, the natural number that n is >=0.
The bisphenol A type epoxy resin is preferably bisphenol A type epoxy resin E51.
In a preferred embodiment in accordance with the present invention, the reactive diluent be selected from epoxy alkyl chloride, alkyl chloride, ketone,
One or more of with heteroaromatic compound, wherein the epoxy alkyl chloride is preferably epoxy chloroethanes or epoxy chloropropionate
Alkane, the alkyl chloride are preferably dichloromethane or chloroform, and the ketone is preferably acetone, and the heteroaromatic compound is preferred
For tetrahydrofuran.
It is highly preferred that the reactive diluent is epoxy alkyl chloride, such as epoxy chloroethanes or epoxychloropropane.
In a preferred embodiment in accordance with the present invention, the cationic visible light solidified composition includes following weight
The component of proportion:
Preferably, the composition includes the component of following weight proportion:
In a preferred embodiment in accordance with the present invention, the preparation method of the cationic visible light solidified composition is such as
Under:
The cation light initiator, sensitizer and reactive diluent are mixed under the conditions of being protected from light, stirring to initiator
It is completely dissolved, bisphenol A type epoxy resin is then added, is kept in dark place after mixing evenly.
The cationic visible light solidified composition provided by the invention is in the visible light source that wavelength is 380~600nm
Polymerization reaction, curing molding can occur under irradiation, and be less than 30mW/cm2Low-light (level) under its solidify conversion ratio up to 50%.
The visible light source can for one of xenon lamp, dysprosium lamp, halogen lamp, tungsten sodium lamp, LED light, laser, natural light or
A variety of, optimal wavelength is 450~550nm.
Agents useful for same, instrument source are as follows in embodiment and experimental example:
Bisphenol type epoxy performed polymer E51, Jiangsu Miki Group；
Halogen lamp (50W, λ=380~580nm), Suzhou Hui Yi industrial materials Co., Ltd；
Illumination photometer, photoelectric instrument factory, Beijing Normal University；
Infrared spectrometer (5700), Nicolet company, the U.S..
Embodiment
The preparation of 1 BODIPY dyestuff -1 of embodiment
Preparation BODIPY dyestuff -1 (being denoted as BPY-1) as shown in formula (IV): taking 500mL single port bottle, by 2mmol pyrroles and
1mmol p-bromobenzaldehyde is dissolved in 200mL methylene chloride, with the air in argon gas displacement flask, and with the side of bubbling argon
Method drives the air in solution out of, then instills a drop trifluoroacetic acid and makees catalyst, persistently stirs under protection of argon gas, reaction temperature
Degree is room temperature (25 DEG C).Reaction is terminated after 2 hours, reaction solution is washed twice with the NaOH solution 100mL of 0.l mol/L, so
Afterwards with the dry organic layer of anhydrous sodium sulfate, methylene chloride is all steamed under the protection of argon gas, is then added
20mL toluene dissolves the residue being evaporated, and reaction mixing is added as oxidant in chloro- 5, the 6- dicyano benzoquinone of l mmol2,3- bis-
In object, 8mmol boron trifluoride ether solution and 8mmol triethylamine are added in reaction system simultaneously after ten minutes, persistently stirred
Silica gel post separation is used after mixing 2 hours, silica gel particle size is 200-300 mesh, and the proportion of eluant, eluent is petroleum ether/positive acetic acid second
Ester (volume ratio)=9:1 obtains maroon crystal, yield 41%.
Using nuclear magnetic resonance spectroscopy (1H-NMR), carbon spectrum (13C-NMR) and flight time mass spectrum (TOF-MS) is to above-mentioned product
Structural Identification is carried out, as a result as follows:
1H-NMR(400MHz,CDCl3): δ=7.96 (s, 2H), 7.69 (d, J=8.4Hz, 2H), 7.45 (d, J=
8.4Hz, 2H), 6.91 (d, J=4.1Hz, 2H), 6.56 (d, J=3.7Hz, 2H)；
13C-NMR(101MHz,CDCl3): δ=145.77,144.59,134.70,132.63,131.84,131.32,
125.52,118.83；
TOF-MS-ES+:347.0169,C15H10N2BBrF2Molecular weight 346.0088.
The above results show that the product being prepared according to 1 the method for the embodiment of the present invention is as shown in formula (IV)
BODIPY dyestuff -1.
The preparation of 2 BODIPY dyestuff -2 of embodiment
Preparation BODIPY dyestuff -2 (being denoted as BPY-2) as shown in formula (V): taking 500mL single port bottle, by 2mmol pyrroles and
1mmol is dissolved in 200mL methylene chloride hexyloxybenzaldehyde, with the air in argon gas displacement flask, and uses bubbling argon
Method the air in solution is driven out of, then instill one drop trifluoroacetic acid make catalyst, persistently stir under protection of argon gas, instead
Answering temperature is room temperature (25 DEG C).Reaction is terminated after 2 hours, and reaction solution is washed two with the NaOH solution 100mL of 0.l mol/L
Time, then with the dry organic layer of anhydrous sodium sulfate, methylene chloride is all steamed under the protection of argon gas, is then added again
Enter 20mL toluene to dissolve the residue being evaporated, chloro- 5, the 6- dicyano benzoquinone of l mmol2,3- bis- is added reaction as oxidant and mixes
It closes in object, 8mmol boron trifluoride ether solution and 8mmol triethylamine is added in reaction system simultaneously after ten minutes, continued
Use silica gel post separation after stirring 2 hours, silica gel particle size is 200-300 mesh, the proportion of eluant, eluent be methylene chloride/just oneself
Alkane (volume ratio)=1:2, obtains orange red solid intermediate.125mL single port bottle is taken, CCl is added in 1.5mmol intermediate4
In (50mL) solution, 1.5mmol N- bromo-succinimide and 0.1mmol benzoyl peroxide are then added, nitrogen is protected
Strong stirring 6h under shield, counterflow condition.It rotates and is concentrated by evaporation under crude product vacuum, silicagel column separating-purifying (hexamethylene/dichloromethane
Alkane (volume ratio)=5:1), obtain red solid, yield 47%.
Using nuclear magnetic resonance spectroscopy (1H-NMR), carbon spectrum (13C-NMR) and flight time mass spectrum (TOF-MS) is to above-mentioned product
Structural Identification is carried out, as a result as follows:
1H-NMR(400MHz,CDCl3): δ=7.94 (d, J=21.4Hz, 1H), 7.76 (s, 1H), 7.52 (dd, J=
8.3,6.3Hz, 2H), 7.11-6.90 (m, 4H), 6.64-6.51 (m, 1H), 4.05 (t, J=6.5Hz, 2H), 1.92-1.76
(m,2H),1.59–1.28(m,6H),0.97–0.86(m,3H)；
13C-NMR(101MHz,CDCl3): δ=162.16,145.25,143.30,141.34,132.91,132.51,
130.11,125.59,119.22,114.76,114.55,105.64,68.45,31.55,29.10,25.70,22.60,
14.03；
TOF-MS-ES+:449.1040,C21H22N2OBBrF2Molecular weight 446.0977.
The above results show that the product being prepared according to 2 the method for the embodiment of the present invention is as shown in formula (V)
BODIPY dyestuff -2.
The preparation (one) of 3 cationic visible light solidified composition of embodiment
0.2000g (0.469mmol) diphenyl iodine hexafluorophosphate (IPF) is weighed, 0.1000g is added
BODIPY dyestuff -1 (BPY-1) made from (0.289mmol) embodiment 1 is placed in brown bottle, and 2mL epoxy chloropropionate is then added
Alkane, being sufficiently stirred is completely dissolved initiator, adds 10g bisphenol type epoxy performed polymer E51, stirs evenly, obtain the sun
Ionic visible light solidified composition, is kept in dark place.
The preparation (two) of 4 cationic visible light solidified composition of embodiment
It is prepared according to method described in the embodiment of the present invention 3 is similar to, difference is only that: by BODIPY dyestuff -1
(BPY-1) 0.1288g (0.289mmol) BODIPY dyestuff -2 (BPY-2) is replaced with.
Comparative example
Comparative example 1
It is prepared according to method described in the embodiment of the present invention 3 is similar to, difference is only that: being added without BODIPY dye
Expect -1 (BPY-1), that is, is added without sensitizer.
Comparative example 2
It is prepared according to method described in the embodiment of the present invention 3 is similar to, difference is only that: being added without diphenyl iodine
Hexafluorophosphate (IPF), that is, be added without cation light initiator.
Experimental example
Experimental example 1
3 × 10 are prepared respectively-6The diphenyl iodine hexafluorophosphate (IPF) of mol/L, BODIPY dyestuff -1 (BPY-1) and
The dichloromethane solution of BODIPY dyestuff -2 (BPY-2) uses the suction of uv-visible absorption spectra instrument measurement above three sample
Receive the curve of spectrum, 400~600nm of wave-length coverage, the result is shown in Figure 1.
As shown in Figure 1, IPF 400nm or more visible region without absorption；And BPY-1 and BPY-2 has in visible region
Relatively strong to absorb, maximum absorption band is near 510nm.
Experimental example 2
Cationic visible light solidified composition sample made from embodiment 3~4 and comparative example 1~2 is evenly coated in two
In rubber ring (diameter is fixed) between sheet glass, pass through 50W halogen lamp (λ=380~580nm, illumination 25.0mW/cm2)
It irradiates at room temperature, each sample repeats experiment three times by infrared diaphanoscopy.It should be noted that same sample point is in halogen lamp
Under irradiation at regular intervals is primary carries out an infrared scan immediately.
Bisphenol type epoxy performed polymer epoxide epoxy group group is monitored in 6072cm by Fourier transform near infrared spectrum-1Near
The characteristic peak at place with light application time variation, and be calculated as follows solidification conversion ratio (that is: epoxy conversion ratio):
Epoxy conversion ratio=[1- (St/Rt)/(S0/R0)] × 100%
Wherein, StCorresponding epoxy group characteristic peak area when being light application time t；
RtCorresponding reference peak area when being light application time t；
S0Corresponding epoxy group characteristic peak area when being t=0；
R0It is reference peak area corresponding to t=0.
The epoxy conversion ratio under different light application times is calculated separately, it is bent with the variation of light application time to draw epoxy conversion ratio
Line is shown in Fig. 2.
As shown in Fig. 2, in 25.0mW/cm2Under the irradiation of illumination halogen lamp (λ=380~580nm):
Photopolymerization reaction can occur for composition made from embodiment 3 (2wt%IPF, 1wt%BPY-1), curing molding,
Epoxy conversion ratio reaches 50%；
Photopolymerization reaction can occur for composition made from embodiment 4 (2wt%IPF, 1wt%BPY-2), curing molding,
Epoxy conversion ratio reaches 40% or more；
Photopolymerization reaction can occur for composition made from comparative example 1 (2wt%IPF, be free of sensitizer), curing molding,
Epoxy conversion ratio significantly reduces, and is no more than 20%；
Photopolymerization reaction cannot occur for composition made from comparative example 2 (1wt%BPY-1 is free of cation light initiator).
Experimental example 3
Cationic visible light solidified composition sample made from embodiment 3~4 and comparative example 1 is evenly coated in two panels glass
In rubber ring (diameter is fixed) between glass, pass through 50W halogen lamp (λ=380~580nm, illumination 15.0mW/cm2) placing
It is irradiated at room temperature after narrow band filter λ=540nm, each sample repeats experiment three times by infrared diaphanoscopy.It needs to illustrate
, the primary infrared scan of progress immediately of same sample point irradiation at regular intervals under halogen lamp.
Bisphenol type epoxy performed polymer epoxide epoxy group group is monitored in 6072cm by Fourier transform near infrared spectrum-1Near
The characteristic peak at place is with the variation of light application time, and calculating solidification conversion ratio by formula described in experimental example 2, (that is: epoxy converts
Rate), and epoxy conversion ratio is drawn with the change curve of light application time, see Fig. 3.
As shown in figure 3, in 15.0mW/cm2Under the irradiation of illumination halogen lamp (λ=540nm):
Photopolymerization reaction can occur for composition made from embodiment 3 (2wt%IPF, 1wt%BPY-1), curing molding,
Epoxy conversion ratio is close to 30%；
Photopolymerization reaction can occur for composition made from embodiment 4 (2wt%IPF, 1wt%BPY-2), curing molding,
Epoxy conversion ratio reaches 15% or more；
Photopolymerization reaction cannot occur for composition made from comparative example 1 (2wt%IPF is free of sensitizer).
Preferred embodiment and exemplary example is combined to describe the invention in detail above.But need to state
It is that these specific embodiments are only not constitute any limit to protection scope of the present invention to illustrative explanations of the invention
System.Without departing from spirit of that invention and protection scope, the technology of the present invention content and embodiments thereof can be carried out
Various improvement, equivalencing or modification, these fall within the protection scope of the present invention.Protection scope of the present invention is with appended power
Subject to benefit requires.
Claims (5)
1. a kind of cationic visible light solidified composition, which is characterized in that the component including following weight proportion:
0.5~10 parts by weight of initiator；
0.5~30 parts by weight of reactive diluent；With
70~90 parts by weight of bisphenol A type epoxy resin,
Wherein, the initiator includes cation light initiator and sensitizer,
The cation light initiator is the diaryl iodonium salt as shown in formula (I),
Wherein, R1Selected from-H ,-R ' and-OR ', R ' be C1-12Alkyl；
X-Selected from SbF6 -, AsF6 -, PF6 -And BF4 -,
The sensitizer has the structure as shown in formula (II),
Wherein, R2、R3、R4Selected from-H ,-R " ,-OR " and-Br, and R2、R3、R4In at least one be-Br, R " be C1-12Alkane
Base,
The weight ratio of the cation light initiator and sensitizer is 1:(0.01~1),
The reactive diluent is selected from epoxy alkyl chloride,
The epoxide number of the bisphenol A type epoxy resin is 0.35~0.57,
Under visible light source irradiation polymerization reaction occurs for the composition, curing molding,
The wavelength of the visible light source is 380~600nm.
2. composition according to claim 1, which is characterized in that the weight ratio of the cation light initiator and sensitizer
For 1:(0.05~0.8).
3. composition according to claim 1, which is characterized in that the weight ratio of the cation light initiator and sensitizer
For 1:(0.25~0.5).
4. composition according to claim 1, which is characterized in that the epoxide number of the bisphenol A type epoxy resin is 0.41
~0.52.
5. according to claim 1 to composition described in one of 4, which is characterized in that the component including following weight proportion:
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| CN108535959B (en) * | 2018-02-28 | 2021-09-24 | 苏州城邦达益材料科技有限公司 | Photosensitive adhesive and preparation method and application thereof |
| CN108912308B (en) * | 2018-06-15 | 2020-09-18 | 天津理工大学 | Double-component cationic visible light initiator and application thereof in photocuring |
| CN109535348B (en) * | 2018-11-26 | 2021-05-18 | 天津理工大学 | Acrylate monomer and photoreactive epoxide initiated by diphenyl iodonium salt and free radical photoinitiator |
| CN113214720A (en) * | 2021-04-28 | 2021-08-06 | 深圳永昌和科技有限公司 | Cationic photopolymer and method for changing cationic photopolymerization conversion rate thereof under action of magnetic field |
| CN114015395A (en) * | 2021-11-11 | 2022-02-08 | 南京艾布纳密封技术股份有限公司 | Light-cured epoxy adhesive and preparation method thereof |
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Inventor after: Chen Yu Inventor after: Zhao Bei Inventor after: Zhang Yufei Inventor after: Lu Ziyi Inventor after: Cheng Xinli Inventor before: Chen Yu Inventor before: Zhao Bei Inventor before: Zhang Yufei Inventor before: Lu Ziyi |